Compound and Organic Electronic Device Comprising the Same

ABSTRACT

The present invention relates to an organic electronic device and a compound comprised therein wherein the compound is represented by the Formula (I): HAr-L-Ar1—(—R1)m.

The present invention relates to a compound and an organic electronicdevice comprising the same. The invention further relates to a displaydevice or a lighting device comprising the organic electronic device.

BACKGROUND ART

Organic light-emitting diodes (OLEDs), which are self-emitting devices,have a wide viewing angle, excellent contrast, quick response, highbrightness, excellent driving voltage characteristics, and colorreproduction. A typical OLED includes an anode, a hole transport layer(HTL), an emission layer (EML), an electron transport layer (ETL), and acathode, which are sequentially stacked on a substrate. In this regard,the HTL, the EML, and the ETL are thin films formed essentially byorganic and/or organometallic compounds.

When a voltage is applied to the anode and the cathode, holes injectedfrom the anode electrode move to the EML, via the HTL, and electronsinjected from the cathode electrode move to the EML, via the ETL. Theholes and electrons mainly recombine in the EML to generate excitons.When the excitons drop from an excited state to a ground state, light isemitted. The injection and flow of holes and electrons should bebalanced, so that an OLED having the above-described structure hasexcellent efficiency.

A variety of organic light-emitting diodes and materials for preparingthe same is known in the art. Nevertheless, there is still a need toImprove the electronic properties of a respective compound for use inorganic electronic devices, in particular to provide a compound suitableto improve the performance of OLEDs, in particular with respect tolifetime and efficiency thereof.

It is, therefore, the object of the present invention to provide novelcompounds for use in organic electronic devices overcoming drawbacks ofthe prior art, in particular compounds suitable to improve theperformance of organic electronic devices with respect to lifetimeand/or efficiency.

The above object is achieved by an organic electronic device comprisingan anode, a cathode, a photoactive layer and an organic semiconductivelayer, wherein the organic semiconductive layer is arranged between thephotoactive layer and the cathode, wherein the organic semiconductivelayer comprises a compound represented by the following formula (I):

HAr-L-Ar₁—(—R¹)_(m)  (I)

-   -   wherein HAr is a group represented by one of the following        formulas (II to IV)

wherein the asterisk symbol “*” represents the binding position of thegroup HAr to the moiety L and;wherein X may be the same or different from each other and areindependently selected from O and S;

-   -   L is selected from the group consisting of unsubstituted or        substituted C₆ to C₂₄ arylene and unsubstituted or substituted        C₃ to C₂₄ heteroarylene, wherein the one or more substituents,        if present, are independently selected from the group consisting        of hydrogen, C₆ to C₁₈ aryl, C₃ to C₄ heteroaryl, D, F, CN, C₁        to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆        alkoxy, C₁ to C₁₇ alkoxy, C₁ to C₁₆ alkoxy, nitrile and        —PO(R³)₂, wherein R³ are independently selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ artl or C₃ to C₂₅ heteroaryl;    -   Ar₁ is selected from the group consisting of C₆ to C₆₀ arylene,        C₃ to C₅₀ heteroarylene containing at least one heteroatom        selected from O, N, S, Si and P, and the following groups        represented by the formulas V to VII;

and the one or more R¹ and R² re independently selected from the groupconsisting of hydrogen, C₆ to C₂₈ aryl, C₃ to C₂₅ heteroaryl, D, F, CN,C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, C₁to C₁₆ alkoxy, C₁ to C₁₆ alkoxy, nitrile and —PO(R³)₂, wherein the groupR³ is selected from C₁ to C₆ alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅heteroaryl; wherein

-   -   m is an integer from 0 to 5;    -   n is independently an integer from 0 to 4; and        wherein if one or more of HAr, Ar¹, L, R¹, R² and R³ and        substituent on one or more of HAr, Ar¹, and L is a carbon        containing group comprising at least one carbon atom directly        connected with at least one hydrogen atom, the hydrogen atoms        comprised in the carbon-containing group may be partially or        fully replaced by deuterium atoms and/or fluorine atoms.

It was surprisingly be found by the inventors that organic electronicdevices in accordance with the present disclosure, i.e. comprising anorganic semiconducting layer comprising or made of a compoundrepresented by Formula (I) are suitable to improve the lifetime (LT97,30 mA/cm²) of the respective device. Furthermore, it was surprisinglyfound that using compounds in accordance with the above Formula (I)together with appropriate dopants, such as UQ results in improvedlifetime and efficiency of organic electronic devices comprising such acombination.

The compounds of Formula (I) containing bisbenzofuropyridine orbisbenzothienopyridine units provide matrix compounds, which haveimproved life time (LT97, 30 mA/cm²) with comparable efficiency ascompared to the material known in the art.

The organic electronic device may be an organic light emitting device(OLED). In this case, the photoactive layer may be the light emittinglayer of the OLED. Likewise, it may be provided that the organicelectronic device is a solar cell. In this case, the photoactive layermay be the light-absorbing layer thereof.

The organic semiconductive layer may be an electron transport layerand/or an electron injection layer. In this way, particular advantagesregarding the lifetime of the organic electronic device may be achieved.

The organic semiconductive layer may further comprise a metal, a metalsalt, an organic alkali metal complex or a mixture thereof. In this way,particular advantages regarding the lifetime of the organic electronicdevice may be achieved.

The organic semiconductive layer may be non-emissive. In this way,particular advantages regarding the lifetime of the organic electronicdevice may be achieved.

The organic semiconductive layer may be an auxiliary electron transportlayer (a-ETL). In this way, particular advantages regarding the lifetimeof the organic electronic device may be achieved.

In the Formulas II to IV both X may be the same and may be selected fromO or S. In this way, particular advantages regarding the lifetime of theorganic electronic device may be achieved.

In the Formulas II to IV both X may be different from each other and oneX is O and the other X is S. In this way, particular advantagesregarding the lifetime of the organic electronic device may be achieved.

L may be selected from unsubstituted or substituted C₆ to C₂₄ aryleneand unsubstituted or substituted C₃ to C₂₄ heteroarylene. In this way,particular advantages regarding the lifetime of the organic electronicdevice may be achieved.

It may be provided that L is selected from substituted or unsubstitutedphenylene, substituted or unsubstituted biphenylene, substituted orunsubstituted terphenylene, substituted or unsubstituted naphthylene,substituted or unsubstituted phenanthrylene, substituted orunsubstituted triphenylene, substituted or unsubstituted anthracenylene.In this way, particular advantages regarding the lifetime of the organicelectronic device may be achieved.

Furthermore, it may be provided that L is selected from one of thefollowing Formulas

R¹ may be selected from the group consisting of hydrogen, C₆ to C_(a)aryl, C₃ to C₂₅ heteroaryl, F, CN and PO(R³)₂, wherein R³ is selectedfrom C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅ heteroaryl. In thisway, particular advantages regarding the lifetime of the organicelectronic device may be achieved.

It may be provided that the Group R, is selected from hydrogen, CN orone of the following structures.

In this regard, it may further provided that Ar₁ may be selected fromthe group consisting of C₆ to C₃₆ arylene, C₃ to C₃₀ heteroarylenecontaining at least one heteroatom selected from O, N, S, Si and P.

In this regard, it may further provided that Ar₁ is independentlyselected from the group consisting of phenylene, naphthylene,phenanthrylene, anthracenylene, fluoranthenylene, pyrenylene,fluoenylene, pyridinylene, bipyridinylene, terpyridinylene,phenanthrolinylene, pyrimidinylene, pyrazinylene, triazinylene,quinolinylene, benzoquinolinylene, quinoxalinylene,benzoquinoxalinylene, acridinylene, benzoacridinylene,dibenzoacridinylene, phenanthrolinylene, carbazolenylene,dibenzofuranenylene, dibenzothiophenylene, benzofuropyrimidinylene,benzothienopyrimidinylene.

Ar₁ may be selected from the group of compounds represented by theformulas V to VII

wherein the asterisk symbol “*” represents the binding position of thegroup Ar₁ to the moiety L and R¹.

In this way, particular advantages regarding the lifetime of the organicelectronic device may be achieved.

m may be an integer from 1 to 4, alternatively m may be an integer from1 to 3. In this way, particular advantages regarding the lifetime of theorganic electronic device may be achieved.

It may be provided that the compound of Formula (I) is selected from thefollowing

The object is further achieved by a compound represented by thefollowing formula (I)

HAr-L-Ar₁—(—R¹)  (I)

-   -   wherein HAr is a group represented by one of the following        formulas (II to IV)

wherein the asterisk symbol “*” represents the binding position of thegroup HAr to the moiety L and;wherein X may be the same or different from each other and areindependently selected from O and S;

-   -   L is selected from the group consisting of unsubstituted or        substituted C₆ to C₂₄ arylene and unsubstituted or substituted        C₃ to C₂₄ heteroarylene, wherein the one or more substituents,        if present, are independently selected from the group consisting        of hydrogen, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, D, F, CN, C₁        to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆        alkoxy, C₁ to C₁₇ alkoxy, C₁ to C₁₆ alkoxy, nitrile and        —PO(R³)₂, wherein Rare independently selected from C₁ to C₁₆        alkyl, C₆ to C₁₈ aryl or C₃ to C₂₅ heteroaryl;        Ar₁ is selected from the group consisting of C₆ to C₆₀ arylene,        C₃ to C₅₀ heteroarylene containing at least one heteroatom        selected from O, N, S, Si and P, and the following groups        represented by the formulas V to VII;

and the one or more R¹ and R² are independently selected from the groupconsisting of hydrogen, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, D, F, CN,C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl C₁ to C₁₆ alkoxy, C₁to C₆ alkoxy, C₁ to C₆ alkoxy, nitrile and —PO(R³)₂, wherein the groupR³ is selected from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅heteroaryl;

-   -   m is an integer from 0 to 5;    -   n is independently an integer from 0 to 4; and        wherein if one or more of HAr, Ar¹, L, R¹, R² and R³ and        substituent on one or more of HAr, Ar¹, and L is a carbon        containing group comprising at least one carbon atom directly        connected with at least one hydrogen atom, the hydrogen atoms        comprised in the carbon-containing group may be partially or        fully replaced by deuterium atoms and/or fluorine atoms.        provided that if L is a trivalent group than the compound of        formula (I) is not symmetrical; and        provided that if Ar₁ is a carbazolylene group than L is not        phenylene.

In this regard, it may be provided that in the Formulas II to IV both Xare the same and selected from O or S.

It may further be provided that in the Formulas II to IV both X aredifferent from each other and one X is O and the other X is S.

In this regard, it may be further provided that L is selected fromunsubstituted or substituted C₆ to C₂₄ arylene and unsubstituted orsubstituted C₃ to C₂₄ heteroarylene.

In this regard, it may further provided that Ar₁ may be selected fromthe group consisting of C₆ to C₃₆ arylene, C₃ to C₃₀ heteroarylenecontaining at least one heteroatom selected from O, N, S, Si and P.

In this regard, it may further provided that Ar₁ is independentlyselected from the group consisting of phenylene, napthylene,phenantrhylene, anthracenylene, fluoranthenylene, pyrenylene,fluoenylene, pyridinylene, bipyridinylene, terpyridinylene,phenanthrolinylene, pyrimidinylene, pyrazinylene, triazinylene,quinolinylene, benzoquinolinylene, quinoxalinylene,benzoquinoxalinylene, acridinylene, benzoacridinylene,dibenzoacridinylene, phenanthrolinylene, carbazolenylene,dibenzofuranenylene, dibenzothiophenylene, benzofuropyrimidinylene,benzothienopyrimidinylene.

In this regard, it may be further provided that Ar₁ is selected from thegroup of compounds represented by the formulas V to VII

Furthermore m may be an integer from 1 to 4, alternatively n may be aninteger from 1 to 3.

Further Layers

In accordance with the invention, the organic electronic device maycomprise, besides the layers already mentioned above, further layers.Exemplary embodiments of respective layers are described in thefollowing:

Substrate

The substrate may be any substrate that is commonly used inmanufacturing of, electronic devices, such as organic light-emittingdiodes. If light is to be emitted through the substrate, the substrateshall be a transparent or semitransparent material, for example a glasssubstrate or a transparent plastic substrate. If light is to be emittedthrough the top surface, the substrate may be both a transparent as wellas a non-transparent material, for example a glass substrate, a plasticsubstrate, a metal substrate or a silicon substrate.

Anode Electrode

Either a first electrode or a second electrode comprised in theinventive organic electronic device may be an anode electrode. The anodeelectrode may be formed by depositing or sputtering a material that isused to form the anode electrode. The material used to form the anodeelectrode may be a high work-function material, so as to facilitate holeinjection. The anode material may also be selected from a low workfunction material (i.e. aluminum). The anode electrode may be atransparent or reflective electrode. Transparent conductive oxides, suchas indium tin oxide (ITO), indium zinc oxide (IZO), tin-dioxide (SnO₂),aluminum zinc oxide (AlZO) and zinc oxide (ZnO), may be used to form theanode electrode. The anode electrode may also be formed using metals,typically silver (Ag), gold (Au), or metal alloys.

Hole Injection Layer

A hole injection layer (HIL) may be formed on the anode electrode byvacuum deposition, spin coating, printing, casting, slot-die coating,Langmuir-Blodgett (LB) deposition, or the like. When the HIL is formedusing vacuum deposition, the deposition conditions may vary according tothe compound that is used to form the HIL and the desired structure andthermal properties of the HIL. In general, however, conditions forvacuum deposition may include a deposition temperature of 100° C. to500° C., a pressure of 10-8 to 10-3 Torr (1 Torr equals 133.322 Pa), anda deposition rate of 0.1 to 10 nm/sec.

When the HIL is formed using spin coating or printing, coatingconditions may vary according to the compound that is used to form theHIL, and the desired structure and thermal properties of the HIL. Forexample, the coating conditions may include a coating speed of about2000 rpm to about 5000 rpm, and a thermal treatment temperature of about80° C. to about 200° C. Thermal treatment removes a solvent after thecoating is performed.

The HIL may be formed of any compound that is commonly used to form aHIL. Examples of compounds that may be used to form the HIL include aphthalocyanine compound, such as copper phthalocyanine (CuPc),4,4′,4″-tris (3-meth)phenylphenylamino) triphenylamine (m-MTDATA),TDATA, 2T-NATA, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA),poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS),polyaniline/camphor sulfonic acid (Pani/CSA), andpolyaniline)/poly(4-styrenesulfonate (PANI/PSS).

The HIL may comprise, or consist of, a p-type dopant and the p-typedopant may be selected from tetrafluoro-tetracyanoquinonedimethane(F4TCNQ), 2,2′-(perfluoronaphthalen-2,6-diylidene) dimalononitrile or2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrlle)but not limited hereto. The HIL may be selected from a hole-transportingmatrix compound doped with a p-type dopant. Typical examples of knowndoped hole transport materials are: copper phthalocyanine (CuPc), whichHOMO level is approximately −5.2 eV, doped withtetrafluoro-tetracyanoquinonedimethane (F4TCNQ), which LUMO level isabout −5.2 eV; zinc phthalocyanine (ZnPc) (HOMO=−5.2 eV) doped withF4TCNQ; α-NPD (N,N′-Bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine)doped with F4TCNQ. α-NPD doped with2,2′-(perfluoronaphthalen-2,6-diylidene) dimalononitrile. The p-typedopant concentrations may be selected from 1 to 20 wt.-%, morepreferably from 3 wt.-% to 10 wt-%.

The thickness of the HIL may be in the range from about 1 nm to about100 nm, and for example, from about 1 mm to about 25 nm. When thethickness of the HIL is within this range, the HIL may have excellenthole injecting characteristics, without a substantial penalty in drivingvoltage.

Hole Transport Layer

A hole transport layer (HTL) may be formed on the HIL by vacuumdeposition, spin coating, slot-die coating, printing, casting,Langmuir-Blodgett (LB) deposition, or the like. When the HTL is formedby vacuum deposition or spin coating, the conditions for deposition andcoating may be similar to those for the formation of the HIL. However,the conditions for the vacuum or solution deposition may vary, accordingto the compound that is used to form the HTL.

The HTL may be formed of any compound that is commonly used to form aHTL. Compounds that can be suitably used are disclosed for example inYasuhiko Shirota and Hiroshi Kageyama, Chem. Rev. 2007, 107, 953-1010and incorporated by reference. Examples of the compound that may be usedto form the HTL are: carbazole derivatives, such as N-phenylcarbaaole orpolyvinylcarbazole; benzidine derivatives, such asN,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine(TPD), or N,N-di(naphthalen-1-yn)-N,N′-diphenyl benzidine (alpha-NPD);and triphenylamine-based compound, such as4,4′,4″-tris(N-carbazolyl)triphnylamine CCA). Among these compounds,TCrA can transport holes and inhibit excitons from being diffused intothe EML.

The thickness of the HTL may be in the range of about 5 nm to about 250nm, preferably, about 10 nm to about 200 nM, further about 20 nm toabout 190 nm, further about 40 nm to about 180 nm, further about 60 nmto about 170 nm, further about 80 nm to about 160 nm, further about 100nm to about 160 nm, further about 120 nm to about 140 nm.

When the thickness of the HTL is within this range, the HTL may haveexcellent hole transporting characteristics, without a substantialpenalty in driving voltage.

Electron Blocking Layer

The function of an electron blocking layer (EBL) is to prevent electronsfrom being transferred from an emission layer to the hole transportlayer and thereby confine electrons to the emission layer. Thereby,efficiency, operating voltage and/or lifetime are improved. Typically,the electron blocking layer comprises a triarylamine compound. Thetriarylamine compound may have a LUMO level closer to vacuum level thanthe LUMO level of the hole transport layer. The electron blocking layermay have a HOMO level that is further away from vacuum level compared tothe HOMO level of the hole transport layer. The thickness of theelectron blocking layer may be selected between 2 and 20 nm.

If the electron blocking layer has a high triplet level, it may also bedescribed as triplet control layer.

The function of the triplet control layer is to reduce quenching oftriplets if a phosphorescent green or blue emission layer is used.Thereby, higher efficiency of light emission from a phosphorescentemission layer can be achieved. The triplet control layer is selectedfrom compounds with a triplet level above the triplet level of thephosphorescent emitter in the adjacent emission layer. Suitablecompounds for the triplet control layer, in particular the triarylaminecompounds, are described in EP 2 722 908 A1.

Emission Layer (EML)

The EML may be formed on the HTL by vacuum deposition, spin coating,slot-die coating, printing, casting, LB deposition, or the like. Whenthe EML is formed using vacuum deposition or spin coating, theconditions for deposition and coating may be similar to those for theformation of the HIL. However, the conditions for deposition and coatingmay vary, according to the compound that is used to form the EML.

The EML may be formed of a combination of host materials and emitterdopants. The EML may comprise a single host material or a plurality ofhost materials. The EML may comprise a single emitter dopant or aplurality of emitter dopants. Examples of the host materials are Alq3,4,4′-N,N′-dicarbazole-biphenyl (CBP), poly(n-vinylcarbazole) (PVK),9,10-di(naphthalene-2-yl)anthracene (ADN),4,4′,4″-tris(carbazol-9-yl)-triphenylamine (TCTA),1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBI),3-tert-butyl-9,10-di-2-naphthylanthracenee (TBADN), distyrylarylene(DSA) and bis(2-(2-hydroxyphenyl)benzo-thiazolate)zinc (Zn(BTZ)2) or acompound of Formula (I).

In case the EML comprises a plurality of host materials to form a hostmixture the amount of each host material in the mixture of hostmaterials may vary between 0.01 and 99.99 parts by weight.

The emitter dopant may be a phosphorescent or fluorescent emitter.Phosphorescent emitters and emitters which emit light via a thermallyactivated delayed fluorescence (TADF) mechanism may be preferred due totheir higher efficiency. The emitter may be a small molecule or apolymer.

Examples of red emitter dopants are PtOEP, Ir(piq)3, and Btp2lr(acac),but are not limited thereto. These compounds are phosphorescentemitters, however, fluorescent red emitter dopants could also be used.

Examples of phosphorescent green emitter dopants are Ir(ppy)3(ppy=phenylpyridine), (ppy)2(acac), Ir(mpyp)3.

Examples of phosphorescent blue emitter dopants are F2Irpic,(F2ppy)2Ir(tmd) and Ir(dfppz)3 and ter-fluorene. 4.4′-bis(4-diphenylamiostyryl)biphenyl (DPAVBi), 2,5,8,11-tetra-tert-butyl perylene (TBPe)are examples of fluorescent blue emitter dopants.

The amount of the emitter dopant may be in the range from about 0.01 toabout 50 parts by weight, based on 100 parts by weight of the host orhost mixture. Alternatively, the emission layer may consist of alight-emitting polymer. The EML may have a thickness of about 10 nm toabout 100 nm, for example, from about 20 nm to about 60 nm. When thethickness of the EML is within this range, the EML may have excellentlight emission, without a substantial penalty in driving voltage.

Hole Blocking Layer (HBL)

A hole blocking layer (HBL) (=auxiliary layer) may be formed on the EML,by using vacuum deposition, spin coating, slot-die coating, printing,casting, LB deposition, or the like, in order to prevent the diffusionof holes into the ETL. When the EML comprises a phosphorescent dopant,the HBL may have also a triplet exciton blocking function. The holeblocking layer may be the inventive organic semiconducting layercomprising or consisting of the inventive compound represented by thegeneral Formula (I) as defined above.

The HBL may be the layer (or one of several layers) comprising thecompound of formula (I).

The HBL may also be named auxiliary ETL, a-ETL or electron transportlayer 1 (ETL-1)

When the HBL is formed using vacuum deposition or spin coating, theconditions for deposition and coating may be similar to those for theformation of the HIL. However, the conditions for deposition and coatingmay vary, according to the compound that is used to form the HBL. Anycompound that is commonly used to form a HBL may be used. Examples ofcompounds for forming the HBL include oxadiazole derivatives, triazinederivatives, triazole derivatives, and phenanthroline derivatives.

The HBL may have a thickness in the range from about 5 nm to about 100nm, for example, from about 10 nm to about 30 nm. When the thickness ofthe HBL is within this range, the HBL may have excellent hole-blockingproperties, without a substantial penalty in driving voltage.

Electron Transport Layer (ETL)

The OLED according to the present invention may comprise an electrontransport layer (ETL). In accordance with the invention, the electrontransport layer may be the inventive organic semiconducting layercomprising the inventive compound represented by the general Formula (I)as defined above.

The electron transport layer may also be named electron transport layer2 (ETL-2)

According to various embodiments the OLED may comprise an electrontransport layer or an electron transport layer stack comprising at leasta first electron transport layer and at least a second electrontransport layer.

By suitably adjusting energy levels of particular layers of the ETL, theinjection and transport of the electrons may be controlled, and theholes may be efficiently blocked. Thus, the OLED may have long lifetime.

The electron transport layer of the organic electronic device maycomprise the compound represented by general Formula (I) as definedabove as the organic electron transport matrix (ETM) material. Theelectron transport layer may comprise, besides the compound representedby the general Formula (I), further ETM materials known in the art.Likewise, the electron transport layer may comprise as the only electrontransport matrix material the compound represented by general Formula(I). In case that the inventive organic electronic device comprises morethan one electron transport layers, the compound represented by thegeneral Formula (I) may be comprised in only one of the electrontransport layers, in more than one of the electron transport layers orin all of the electron transport layers. In accordance with theinvention, the electron transport layer may comprise, besides the ETMmaterial, at least one additive as defined herein.

Further, the electron transport layer may comprise one or more n-typedopants. The additive may be an n-type dopant. The additive can bealkali metal, alkali metal compound, alkaline earth metal, alkalineearth metal compound, transition metal, transition metal compound or arare earth metal. In another embodiment, the metal can be one selectedfrom a group consisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce,Sm, Eu, Tb, Dy, and Yb. In another embodiment, the n-type dopant can beone selected from a group consisting of Cs, K, Rb, Mg, Na, Ca, Sr, Euand Yb. In an embodiment the alkali metal compound may be8-Hydroxyquinolinolato-lithium (LiQ), Lithiumtetra(1H-pyrazol-1-yl)borate or Lithium 2-(diphenylphosphoryl)phenolate.Suitable compounds for the ETM (which may be used in addition to theinventive compound represented by the general Formula (I) as definedabove) are not particularly limited. In one embodiment, the electrontransport matrix compounds consist of covalently bound atoms.Preferably, the electron transport matrix compound comprises aconjugated system of at least 6, more preferably of at least 10delocalized electrons. In one embodiment, the conjugated system ofdelocalized electrons may be comprised in aromatic or heteroaromaticstructural moieties, as disclosed e.g. in documents EP 1970 371 A1 or WO2013/079217 A1.

Electron Injection Layer (EL)

An optional EIL, which may facilitates injection of electrons from thecathode, may be formed on the ETL, preferably directly on the electrontransport layer. Examples of materials for forming the EL includelithium 8-hydroxyquinolinolate (WQ), LiF, NaCl, CaF, Li₂O, BaO, Ca, Ba,Yb, Mg which are known in the art. Deposition and coating conditions forforming the EIL are similar to those for formation of the HIL, althoughthe deposition and coating conditions may vary, according to thematerial that is used to form the EIL. The EIL may be the organicsemiconducting layer comprising the compound of Formula (I).

The thickness of the EIL may be in the range from about 0.1 nm to about10 nm, for example, in the range from about 0.5 nm to about 9 nm. Whenthe thickness of the EIL is within this range, the EIL may havesatisfactory electron-injecting properties, without a substantialpenalty in driving voltage.

Cathode Electrode

The cathode electrode is formed on the EIL, if present. The cathodeelectrode may be formed of a metal, an alloy, an electrically conductivecompound, or a mixture thereof.

The cathode electrode may have a low work function. For example, thecathode electrode may be formed of lithium (Li), magnesium (Mg),aluminum (Al), aluminum (Al)-lithium (Li), calcium (Ca), barium (Ba),ytterbium (Yb), magnesium (Mg)-indium (In), magnesium (Mg)-silver (Ag),or the like. Alternatively, the cathode electrode may be formed of atransparent conductive oxide, such as TO or IZO.

The thickness of the cathode electrode may be in the range from about 5nm to about 1000 nm, for example, in the range from about to nm to abouttoo nm. When the thickness of the cathode electrode is in the range fromabout 5 nm to about 50 in, the cathode electrode may be transparent orsemitransparent even if formed by a metal or metal alloy.

It is to be understood that the cathode electrode is not part of anelectron injection layer or the electron transport layer.

Charge Generation Layer

The charge generation layer (CGL) may comprise a p-type and an n-typelayer. An interlayer may be arranged between the p-type layer and then-type layer. The CGL may comprise the compound represented by generalFormula (I).

Typically, the charge generation layer is a pn junction joining ann-type charge generation layer (electron generating layer) and a holegenerating layer. The n-side of the pn junction generates electrons andinjects them into the layer which is adjacent in the direction to theanode. Analogously, the p-side of the p-n junction generates holes andinjects them into the layer which is adjacent in the direction to thecathode.

Charge generating layers may be used in tandem devices, for example, intandem OLEDs comprising, between two electrodes, two or more emissionlayers. In a tandem OLED comprising two emission layers, the n-typecharge generation layer provides electrons for the first light emissionlayer arranged near the anode, while the hole generating layer providesholes to the second light emission layer arranged between the firstemission layer and the cathode.

Suitable matrix materials for the hole generating layer may be materialsconventionally used as hole injection and/or hole transport matrixmaterials. Also, p-type dopant used for the hole generating layer canemploy conventional materials. For example, the p-type dopant can be oneselected from a group consisting oftetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), derivatives oftetraqvanoquinodimethane, radialene derivatives, iodine, FeCl3, FeF3,and SbCl5. Also, the host can be one selected from a group consisting ofN,N-di(naphthalen-1-yl)-N,N-diphenyl-benzidine (NPB),N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1-biphenyl-4,4′-liamine (TPD)and N,N′,N′-tetranaphthyl-benzidine (TNB). The p-type charge generationlayer may consist of CNHAT.

The n-type charge generating layer may be the layer comprising thecompound of Formula (I). The n-type charge generation layer can be layerof a neat n-type dopant, for example of an electropositive metal, or canconsist of an organic matrix material doped with the n-type dopant. Inone embodiment, the n-type dopant can be alkali metal, alkali metalcompound, alkaline earth metal, alkaline earth metal compound, atransition metal, a transition metal compound or a rare earth metal. Inanother embodiment, the metal can be one selected from a groupconsisting of Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, La, Ce, Sm, Eu, Tb, Dy,and Yb. More specifically, the n-type dopant can be one selected from agroup consisting of Cs, K, Rb, Mg. Na, Ca, Sr, Eu and Yb. Suitablematrix materials for the electron generating layer may be the materialsconventionally used as matrix materials for electron injection orelectron transport layers. The matrix material can be for example oneselected from a group consisting of triazine compounds, hydroxyquinolinederivatives like tri(8-hydroxyquinoline)aluminum, benzazole derivatives,and silole derivatives.

The hole generating layer is arranged in direct contact to the n-typecharge generation layer.

Organic Light-Emitting Diode (OLED)

The organic electronic device according to the invention may be anorganic light-emitting device.

According to one aspect of the present invention, there is provided anorganic light-emitting diode (OLED) comprising: a substrate; an anodeelectrode formed on the substrate; a hole injection layer, a holetransport layer, an emission layer, an organic semiconducting layercomprising a compound of formula (I) or consisting of a compound ofFormula (I) and a cathode electrode.

According to another aspect of the present invention, there is providedan OLED comprising: a substrate; an anode electrode formed on thesubstrate; a hole injection layer, a hole transport layer, an electronblocking layer, an emission layer, a hole blocking layer, an organicsemiconducting layer comprising a compound of formula (I) or consistingof a compound of Formula (I) and a cathode electrode.

According to another aspect of the present invention, there is providedan OLED comprising: a substrate; an anode electrode formed on thesubstrate; a hole injection layer, a hole transport layer, an electronblocking layer, an emission layer, a hole blocking layer, an organicsemiconducting layer comprising a compound of Formula (I) or consistingof a compound of Formula (I), an electron injection layer, and a cathodeelectrode.

According to various embodiments of the present invention, there may beprovided OLEDs layers arranged between the above mentioned layers, onthe substrate or on the top electrode.

According to one aspect, the OLED can comprise a layer structure of asubstrate that is adjacently arranged to an anode electrode, the anodeelectrode is adjacently arranged to a first hole injection layer, thefirst hole injection layer is adjacently arranged to a first holetransport layer, the first hole transport layer is adjacently arrangedto a first electron blocking layer, the first electron blocking layer isadjacently arranged to a first emission layer, the first emission layeris adjacently arranged to a first electron transport layer, the firstelectron transport layer is adjacently arranged to an n-type chargegeneration layer, the n-type charge generation layer is adjacentlyarranged to a hole generating layer, the hole generating layer isadjacently arranged to a second hole transport layer, the second holetransport layer is adjacently arranged to a second electron blockinglayer, the second electron blocking layer is adjacently arranged to asecond emission layer, between the second emission layer and the cathodeelectrode an optional electron transport layer and/or an optionalinjection layer are arranged.

The organic semiconducting layer according to the invention may be anemission layer, a hole blocking layer, an electron transport layer, afirst electron transport layer, an n-type charge generation layer and/ora second electron transport layer.

For example, the OLED (10) according to FIG. 2 may be formed by aprocess, wherein

on a substrate (10), an anode (120), a hole injection layer (130), ahole transport layer (140), an electron blocking layer (145), anemission layer (150), a hole blocking layer (155), an electron transportlayer (160), an electron injection layer (180) and the cathode electrode(190) are subsequently formed in that order.

Organic Electronic Device

An organic electronic device according to the invention comprises anorganic semiconducting layer comprising a compound according to Formula(I) or consisting of a compound of Formula (I).

An organic electronic device according to one embodiment may include asubstrate, an anode layer, an organic semiconducting layer comprising acompound of Formula (I) or consisting of a compound of Formula (I) and acathode layer.

An organic electronic device according to one embodiment comprises atleast one organic semiconducting layer comprising at least one compoundof Formula (I) or consisting of a compound of Formula (I), at least oneanode layer, at least one cathode layer and at least one emission layer,wherein the organic semiconducting layer is preferably arranged betweenthe emission layer and the cathode layer.

An organic light-emitting diode (OLED) according to the invention mayinclude an anode, a hole transport layer (HTL), an emission layer (EML),an electron transport layer (ETL) comprising at least one compound ofFormula (I), and a cathode, which are sequentially stacked on asubstrate. In this regard, the HTL, the EML, and the ETL are thin filmsformed from organic compounds.

An organic electronic device according to one embodiment can be a lightemitting device, thin film transistor, a battery, a display device or aphotovoltaic cell, and preferably a light emitting device.

According to another aspect of the present invention, there is provideda method of manufacturing an organic electronic device, the methodusing:

-   -   at least one deposition source, preferably two deposition        sources and more preferred at least three deposition sources.

The methods for deposition that can be suitable comprise:

-   -   deposition via vacuum thermal evaporation;    -   deposition via solution processing, preferably the processing is        selected from spin-coating, printing, casting; and/or    -   slot-die coating.

According to various embodiments of the present invention, there isprovided a method using:

-   -   a first deposition source to release the compound of Formula (I)        according to the invention, and    -   a second deposition source to release a metal, a metal complex,        an organo-metallic compound, a metal salt or an alkali or        alkaline earth metal complex; alternatively an organic alkali or        alkaline earth metal complex; alternatively        8-hydroxyquinolinolato lithium or alkali borate;        the method comprising the steps of forming the organic        semiconducting layer; whereby for an organic light-emitting        diode (OLED):    -   the organic semiconducting layer is formed by releasing the        compound of Formula (I) according to the invention from the        first deposition source and a metal, a metal complex, an        organo-metallic compound, a metal salt or an alkali or alkaline        earth metal complex; alternatively an organic alkali or alkaline        earth metal complex; alternatively 8-hydroxyquinolinolato        lithium or alkali borate, from the second deposition source.

According to various embodiments of the present invention, the methodmay further include forming on the anode electrode, an emission layerand at least one layer selected from the group consisting of forming ahole injection layer, forming a hole transport layer, or forming a holeblocking layer, between the anode electrode and the first electrontransport layer.

According to various embodiments of the present invention, the methodmay further include the steps for forming an organic light-emittingdiode (OLED), wherein

-   -   on a substrate a first anode electrode is formed,    -   on the first anode electrode an emission layer is formed,    -   on the emission layer an electron transport layer stack is        formed, optionally a hole blocking layer is formed on the        emission layer and an organic semiconducting layer is formed,    -   and finally a cathode electrode is formed,    -   optional a hole injection layer, a hole transport layer, and a        hole blocking layer, formed in that order between the first        anode electrode and the emission layer,    -   optional an electron injection layer is formed between the        organic semiconducting layer and the cathode electrode.

According to various embodiments of the present invention, the methodmay further comprise forming an electron injection layer on the organicsemiconducting layer. However, according to various embodiments of theOLED of the present invention, the OLED may not comprise an electroninjection layer.

According to various embodiments, the OLED may have the following layerstructure, wherein the layers having the following order:

anode, hole injection layer, first hole transport layer, second holetransport layer, emission layer, optional hole blocking layer, organicsemiconducting layer comprising a compound of Formula (I) according tothe invention, optional electron injection layer, and cathode, oranode, hole injection layer, first hole transport layer, second holetransport layer, organic semicondncting layer comprising a compound ofFormula (I) according to the invention, optional hole blocking layer,first electron transport layer, optional electron injection layer, andcathode, oranode, hole injection layer, first hole transport layer, second holetransport layer, emission layer, organic semiconducting layer comprisinga compound of Formula (I) according to the invention, first electrontransport layer, optional electron injection layer, and cathode.

According to another aspect of the invention, it is provided anelectronic device comprising at least one organic light emitting deviceaccording to any embodiment described throughout this application,preferably, the electronic device comprises the organic light emittingdiode in one of embodiments described throughout this application. Morepreferably, the electronic device is a display device.

In one embodiment, the organic electronic device according to theinvention comprising an organic semiconducting layer comprising acompound according to Formula (I) or consisting of a compound of Formula(I) may further comprise a layer comprising a radialene compound and/ora quinodimethane compound.

In one embodiment, the radialene compound and/or the quinodimethanecompound may be substituted with one or more halogen atoms and/or withone or more electron withdrawing groups. Electron withdrawing groups canbe selected from nitrile groups, halogenated alkyl groups, alternativelyfrom perhalogenated alkyl groups, alternatively from perfluorinatedalkyl groups. Other examples of electron withdrawing groups may be acyl,sulfonyl groups or phosphoryl groups.

Alternatively, acyl groups, sulfonyl groups and/or phosphoryl groups maycomprise halogenated and/or perhalogenated hydrocarbyl. In oneembodiment, the perhalogenated hydrocarbyl may be a perfluorinatedhydrocarbyl. Examples of a perfluorinated hydrocarbyl can beperfluormethyl, perfluorethyl, perfluorpropyl, perfluorisopropyl,perfluorobutyl, perfluorophenyl, perfluorotolyl; examples of sulfonylgroups comprising a halogenated hydrocarbyl may betrifluoromethylsulfonyl, pentafluoroethylsulfonyl,pentafluorophenylsulfonyl, heptafluoropropylsufonyl,nonafluorobutylsulfonyl, and like.

In one embodiment, the radialene and/or the quinodimethane compound maybe comprised in a hole injection, hole transporting and/or a holegeneration layer.

In one embodiment, the radialene compound may have Formula (XX) and/orthe quinodimethane compound may have Formula (XXIa) or (XXb):

wherein R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R¹¹, R¹², R¹⁵, R¹⁶, R²⁰, R²¹ areindependently selected from above mentioned electron withdrawing groupsand R⁹, R¹⁰, R¹³, R¹⁴, R¹⁷, R¹⁸, R¹⁹, R²², R²³ and R²⁴ are independentlyselected from H, halogen and above mentioned electron withdrawinggroups.

Hereinafter, the embodiments are illustrated in more detail withreference to examples. However, the present disclosure is not limited tothe following examples. Reference will now be made in detail to theexemplary aspects.

Details and Definitions of the Invention

In the present specification, when a definition is not otherwiseprovided, an “alkyl group” may refer to an aliphatic hydrocarbon group.The alkyl group may refer to “a saturated alkyl group” without anydouble bond or triple bond. The term “alkyl” as used herein shallencompass linear as well as branched and cyclic alkyl. For example,Ca-alkyl may be selected from n-propyl and iso-propyl. Likewise,C₄-alkyl encompasses n-butyl, sec-butyl and t-butyl. Likewise, C₆-alkylencompasses n-hexyl and cyclo-hexyl.

The subscribed number n in C_(n) relates to the total number of carbonatoms in the respective alkyl, arylene, heteroarylene or aryl group.

The term “aryl” or “arylene” as used herein shall encompass phenyl(C₆-aryl), fused aromatics, such as naphthalene, anthracene,phenanthracene, tetracene etc. Further encompassed are biphenyl andoligo- or polyphenyls, such as terphenyl etc. Further encompassed shallbe any further aromatic hydrocarbon substituents, such as fluorenyl etc.“Arylene” respectively “heteroarylene”, refers to groups to which twofurther moieties are attached. In the present specification the term“aryl group” or “arylene group” may refer to a group comprising at leastone hydrocarbon aromatic moiety, and all the elements of the hydrocarbonaromatic moiety may have p-orbitals which form conjugation, for examplea phenyl group, a naphtyl group, an anthracenyl group, a phananthrenylgroup, a pyrenyl group, a fluorenyl group and the like. The aryl orarylene group may include a monocyclic or fused ring polycyclic (i.e.,rings sharing adjacent pairs of carbon atoms) functional group.

The term “heteroaryl” as used herein refers to aryl groups in which atleast one carbon atom is substituted with a heteroatom, preferablyselected from N, O, S, B or Si.

The subscripted number n in C_(n)-heteroaryl merely refers to the numberof carbon atoms excluding the number of heteroatoms. In this context, itis clear that a C heteroarylene group is an aromatic compound comprisingthree carbon atoms, such as pyrazol, imidazole, oxazole, thiazole andthe like.

The term “heteroaryl” may refer to aromatic heterocycles with at leastone heteroatom, and all the elements of the hydrocarbon heteroaromaticmoiety may have p-orbitals which form conjugation. The heteroatom may beselected from N, O, S, B, Si, P, Se, preferably from N, O and S. Aheteroarylene ring may comprise at least 1 to 3 heteroatoms. Preferablya heteroarylene ring may comprise at least 1 to 3 heteroatomsindividually selected from N, S and/or 0.

The term “heteroaryl” as used herewith shall encompass pyridine,quinoline, quinazoline, pyridine, triazine, benzimidazole,benzothiazole, benzo[4,5]thieno[3,2-d]pyrimidine, carbazole, zanthene,phenoxazine, benzoacridine, dibenzoacridine and the like.

In the present specification, the single bond refers to a direct bond.

The term “fluorinated” as used herein refers to a hydrocarbon group inwhich at least one of the hydrogen atoms comprised in the hydrocarbongroup is substituted by a fluorine atom. Fluorinated groups in which allof the hydrogen atoms thereof are substituted by fluorine atoms arereferred to as perfluorinated groups and are particularly addressed bythe term “fluorinated”.

In terms of the invention, a group is “substituted with” another groupif one of the hydrogen atoms comprised in this group is replaced byanother group, wherein the other group is the substituent.

In terms of the invention, the expression “between” with respect to onelayer being between two other layers does not exclude the presence offurther layers which may be arranged between the one layer and one ofthe two other layers. In terms of the invention, the expression “indirect contact” with respect to two layers being in direct contact witheach other means that no further layer is arranged between those twolayers. One layer deposited on the top of another layer is deemed to bein direct contact with this layer.

With respect to the inventive organic semiconducting layer as well aswith respect to the inventive compound, the compounds mentioned in theexperimental part are most preferred.

The inventive organic electronic device may be an organicelectroluminescent device (OLED) an organic photovoltaic device (OPV), alighting device, or an organic field-effect transistor (OFET). Alighting device may be any of the devices used for illumination,irradiation, signaling, or projection. They are correspondinglyclassified as illuminating, irradiating, signaling, and projectingdevices. A lighting device usually consists of a source of opticalradiation, a device that transmits the radiant flux into space in thedesired direction, and a housing that joins the parts into a singledevice and protects the radiation source and light-transmitting systemagainst damage and the effects of the surroundings.

According to another aspect, the organic electroluminescent deviceaccording to the present invention may comprise more than one emissionlayer, preferably two or three emission layers. An OLED comprising morethan one emission layer is also described as a tandem OLED or stackedOLED.

The organic electroluminescent device (OLED) may be a bottom- ortop-emission device.

Another aspect is directed to a device comprising at least one organicelectroluminescent device (OLED).

A device comprising organic light-emitting diodes is for example adisplay or a lighting panel.

In the present invention, the following defined terms, these definitionsshall be applied, unless a different definition is given in the claimsor elsewhere in this specification.

In the context of the present specification the term “different” or“differs” in connection with the matrix material means that the matrixmaterial differs in their structural Formula.

The terms “OLED” and “organic light-emitting diode” are simultaneouslyused and have the same meaning. The term “organic electroluminescentdevice” as used herein may comprise both organic light emitting diodesas well as organic light emitting transistors (OLETs).

As used herein, “weight percent”, “wt-%”, “percent by weight”, “byweight”, parts by weight and variations thereof refer to a composition,component, substance or agent as the weight of that component, substanceor agent of the respective electron transport layer divided by the totalweight of the respective electron transport layer thereof and multipliedby 100. It is under-stood that the total weight percent amount of allcomponents, substances and agents of the respective electron transportlayer and electron injection layer are selected such that it does notexceed 100 wt.-%.

As used herein, “volume percent”, “vol.-%”, “percent by volume”, “byvolume”, and variations thereof refer to a composition, component,substance or agent as the volume of that component, substance or agentof the respective electron transport layer divided by the total volumeof the respective electron transport layer thereof and multiplied by100. It is understood that the total volume percent amount of allcomponents, substances and agents of the cathode layer are selected suchthat it does not exceed 100 vol.-%.

All numeric values are herein assumed to be modified by the term“about”, whether or not explicitly indicated. As used herein, the term“about” refers to variation in the numerical quantity that can occur.Whether or not modified by the term “about” the claims includeequivalents to the quantities.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a”, “an”, and “the” include plural referentsunless the content dearly dictates otherwise.

The term“free of”, “does not contain”, “does not comprise” does notexclude impurities. Impurities have no technical effect with respect tothe object achieved by the present invention.

In the context of the present specification the term “essentiallynon-emissive” or “non-emissive” means that the contribution of thecompound or layer to the visible emission spectrum from the device isless than 10%, preferably less than 5% relative to the visible emissionspectrum. The visible emission spectrum is an emission spectrum with awavelength of about a 380 nm to about ≤780 nm.

Preferably, the organic semiconducting layer comprising the compound ofFormula (I) is essentially non-emissive or non-emitting.

The operating voltage, also named U, is measured in Volt (V) at 10milliAmpere per square centimeter (mA/cm2).

The candela per Ampere efficiency, also named cd/A efficiency ismeasured in candela per ampere at 10 milliAmpere per square centimeter(mA/cm2).

The external quantum efficiency, also named EQE, is measured in percent(%).

The color space is described by coordinates CIE-x and CIE-y(International Commission on Illumination 1931). For blue emission theCIE-y is of particular importance. A smaller CIE-y denotes a deeper bluecolor.

The highest occupied molecular orbital, also named HOMO, and lowestunoccupied molecular orbital, also named LUMO, are measured in electronvolt (eV).

The term “OLED”, “organic light emitting diode”, “organic light emittingdevice” “organic optoelectronic device” and “organic light-emittingdiode” are simultaneously used and have the same meaning.

The term “life-span” and “lifetime” are simultaneously used and have thesame meaning.

The anode electrode and cathode electrode may be described as anodeelectrode/cathode electrode or anode electrode/cathode electrode oranode electrode layer/cathode electrode layer.

Room temperature, also named ambient temperature, is 23° C.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects and advantages of the present invention willbecome apparent and more readily appreciated from the followingdescription of the exemplary embodiments, taken in conjunction with theaccompanying drawings, of which:

FIG. 1 is a schematic sectional view of an organic light-emitting diode(OLED), according to an exemplary embodiment of the present invention;

FIG. 2 is a schematic sectional view of an OLED, according to anexemplary embodiment of the present invention.

FIG. 3 is a schematic sectional view of a tandem OLED comprising acharge generation layer, according to an exemplary embodiment of thepresent invention.

DETAILED DESCRIPTION

Reference will now be made in detail to the exemplary embodiments of thepresent invention, examples of which are illustrated in the accompanyingdrawings, wherein like reference numerals refer to the like elementsthroughout. The exemplary embodiments are described below, in order toexplain the aspects of the present invention, by referring to thefigures.

Herein, when a first element is referred to as being formed or disposed“on” or “onto” a second element, the first element can be disposeddirectly on the second element, or one or more other elements may bedisposed there between. When a first element is referred to as beingformed or disposed “directly on” or “directly onto” a second element, noother elements are disposed there between.

FIG. 1 is a schematic sectional view of an organic light-emitting diode(OLED) 100, according to an exemplary embodiment of the presentinvention. The OLED 100 includes a substrate 110, an anode 120, a holeinjection layer (HIL) 130, a hole transport layer (HTL) 140, an emissionlayer (EML) 150, an electron transport layer (ETL) 160. The electrontransport layer (ETL) 160 is formed on the EML 150. Onto the electrontransport layer (ETL) 160, an electron injection layer (EIL) 180 isdisposed. The cathode 190 is disposed directly onto the electroninjection layer (EIL) 180.

Instead of a single electron transport layer 160, optionally an electrontransport layer stack (EL) can be used.

FIG. 2 is a schematic sectional view of an OLED 100, according toanother exemplary embodiment of the present invention. FIG. 2 differsfrom FIG. 1 in that the OLED 100 of FIG. 2 comprises an electronblocking layer (EBL) 14 and a hole blocking layer (HBL) 155.

Referring to FIG. 2, the OLED 100 includes a substrate 110, an anode120, a hole injection layer (HIL) 130, a hole transport layer (HTL) 140,an electron blocking layer (EBL) 145, an emission layer (EML) 150, ahole blocking layer (HBL) 155, an electron transport layer (ETL) 160, anelectron injection layer (EIL) 180 and a cathode electrode 190.

Preferably, the organic semiconducting layer comprising a compound ofFormula (I) or consisting of a compound of Formula (I) may be an HBL oran ETL.

FIG. 3 is a schematic sectional view of a tandem OLED 200, according toanother exemplary embodiment of the present invention. FIG. 3 differsfrom FIG. 2 in that the OLED 100 of FIG. 3 further comprises a chargegeneration layer (CGL) and a second emission layer (151).

Referring to FIG. 3, the OLED 200 includes a substrate no, an anode 120,a first hole injection layer (HIL) 130, a first hole transport layer(HTL) 140, a first electron blocking layer (EBL) 145, a first emissionlayer (EML) 150, a first hole blocking layer (HBL) 155, a first electrontransport layer (ETL) 160, an n-type charge generation layer (n-typeCGL) 185, a hole generating layer (p-type charge generation layer;p-type GCL) 135, a second hole transport layer (HTL) 141, a secondelectron blocking layer (EBL) 146, a second emission layer (EML) 151, asecond hole blocking layer (EBL) 156, a second electron transport layer(ETL) 161, a second electron injection layer (EIL) 181 and a cathode190.

Preferably, the organic semiconducting layer comprising a compound ofFormula (I) or consisting of a compound of Formula (I) may be the firstHBL, first ETL, n-type CGL and/or second HBL, second ETL.

While not shown in FIG. 1, FIG. 2 and FIG. 3, a sealing layer mayfurther be formed on the cathode electrodes 190, in order to seal theOLEDs 100 and 200. In addition, various other modifications may beapplied thereto.

Hereinafter, one or more exemplary embodiments of the present inventionwill be described in detail with, reference to the following examples.However, these examples are not intended to limit the purpose and scopeof the one or more exemplary embodiments of the present invention.

Experimental Data Preparation of compounds of formula D Synthesis of6-(4-bromophenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine (3)

A flask was flushed with nitrogen and charged with(Z)-2-(4-bromobenzylidene)benzofuran-3(2H)-one (1) (13 g, 43.2 mmol),benzofuran-3(2H)-one (2) (5.8 g, 43.2 mmol), ammonium acetate (30 g, 389mmol) and glacial acetic acid (195 mL). The mixture was heated to 120°C. under a nitrogen atmosphere for 17 h. After cooling down to 5° C.using an ice bath, the formed precipitate was collected by suctionfiltration and washed with acetic acid, water (until pH neutral) andmethanol. The obtained solid was further purified by recrystallizationfrom DMF. After drying, 9 g of6-(4-bromophenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine (3) wereobtained.

Synthesis of6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(4)

A flask was flushed with nitrogen and charged with6-(4-bromophenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine (6.9 g, 16.7mmol), 4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (3)(4.65 g, 18.3 mmol), Pd(dppf)Cl₂ (0.37 g. 0.5 mmol), and potassiumacetate (4.9 g, 50 mmol). Dry and deaerated DMF (60 mL) was added andthe reaction mixture was heated to go ° C. under a nitrogen atmospherefor 21 h. After cooling down to 5° C. using an ice bath, the formedprecipitate was collected by suction filtration and washed with DMF. Thesolid was dissolved in dichloromethane and the organic phase was washedwith water three times. After drying over MgSO₄, the organic phase wasfiltered through a pad of Florisil After rinsing with additionaldichloromethane, the filtrate was concentrated to a minimal amount andn-hexane was added. The formed precipitate was isolated by suctionfiltration and washed with n-hexane. Further purification was achievedby recrystallization from DMF. After drying, 6 g of6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(4) were obtained.

Synthesis of 6-(3-bromophenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine (6)

6-(3-bromophenyl)bis(benzofuro)[,2-b:2′,3′-e]pyridine (6) wassynthesized using (Z)-2-(3-bromobenzylidene)benzofuran-3(2H)-one (20 g,66.4 mmol) and by following the procedure described for the synthesis of6-(4-bromophenyl)bis(benzo-furo)[3,2-b:2′,3′-e]pyridine (3)

Compounds of formula 1 may be prepared as described below.

General Procedure 1 for the Synthesis of the Compound of Formula (I)

A flask was flushed with nitrogen and charged with compound A (10.9mmol), 4,4,5-tetramethyl-2-(3′,4′, 5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane (7)(7.6 g, 13 mmol),Pd(PPh₃)₄ (0.25 g, 0.22 mmol), and K₂CO₃ (3 g, 21.7 mmol). A mixture ofdeaerated THF/water (4:1, 75 mL) was added and the reaction mixture washeated to reflux under a nitrogen atmosphere for 24 h. Subsequently,additional4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane(1.3 g, 2.2 mmol) and Pd(dppf)Cl₂ (0.04 g, 0.05 mmol) were added and themixture was refluxed for additional 8 h. After cooling down to roomtemperature, the reaction mixture was concentrated under reducedpressure and the formed precipitate was collected by suction filtrationand washed with n-hexane. The obtained solid was dissolved indichloromethane and the organic phase was washed with water three times.After drying over MgSO₄, the organic phase was filtered through a pad ofsilica gel. After rinsing with additional dichloromethane, the filtratewas concentrated to a minimal amount and n-hexane was added. The formedprecipitate was isolated by suction filtration and washed with n-hexane.Further purification was achieved by precipitation of the product from aconcentrated dichloromethane solution by addition of cyclohexane. Afterstirring for 2 h, the resulting precipitate was isolated by suctionfiltration and washed with cyclohexane. After drying compound of formula(I) was obtained. Final purification was achieved by sublimation.

Synthesis of 6-(4′,5′, 6′-triphenyl-[1,1′: 2′,1″:3″,1′″-quaterphenyl]-3′″-yl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine (C1)

Compound C-1 was synthesized by following procedure 1. A flask wasflushed with nitrogen and charged with6-(3-bromophenyl)bis(benzo-furo)[3,2-b:2′,3′-e]pyridine (6) (4.5 g, 10.9mmol),4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane(7) (7.6 g, 13 mmol), Pd(PPh₃)₄ (0.25 g, 0.22 mmol), and K₂CO₃ (3 g,21.7 mmol). A mixture of deaerated THF/water (4:1, 75 mL) was added andthe reaction mixture was heated to reflux under a nitrogen atmospherefor 24 h. Subsequently, additional4,4,5,5-tetramethyl-2-(3′,4′,5′-triphenyl-[1,1′:2′,1″-terphenyl]-3-yl)-1,3,2-dioxaborolane(1.3 g, 2.2 mmol) and Pd(dppf)Cl2 (0.04 g, 0.05 mmol) were added and themixture was refluxed for additional 8 h. After cooling down to roomtemperature, the reaction mixture was concentrated under reducedpressure and the formed precipitate was collected by suction filtrationand washed with n-hexane. The obtained solid was dissolved indichloromethane and the organic phase was washed with water three times.After drying over MgSO₄, the organic phase was filtered through a pad ofsilica gel. After rinsing with additional dichloromethane, the filtratewas concentrated to a minimal amount and n-hexane was added. The formedprecipitate was isolated by suction filtration and washed with n-hexane.Further purification was achieved by precipitation of the product from aconcentrated dichloromethane solution by addition of cyclohexane. Afterstirring for 2 h, the resulting precipitate was isolated by suctionfiltration and washed with cyclohexane. After drying, 6.3 g of6-(4′,5′,6′-triphenyl-[1,1′:2′,1″:3″,1′″-quaterphenyl]-3′″-yl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(C1) were obtained. Final purification was achieved by sublimation.HPLC/ESI-MS: m/z=792 ([M+H]+).

General Procedure 2 for the Synthesis of the Compound of Formula (I)

A flask was flushed with nitrogen and charged with compound B (12.8mmol), 2-([1,1′-biphenyl]-2-yl)-4-chloro-6-phenyl-1,3,5-triazine (8)(4.6 g, 13.4 mmol), Pd(PPh₃)₄ (0.3 g, 0.26 mmol), and K₂CO₂ (3.5 g, 25.6mmol). A mixture of deaerated THF/water (4:1, 50 mL) was added and thereaction mixture was heated to reflux under a nitrogen atmosphere for 21h. After cooling down to 5° C. using an ice bath, the formed precipitatewas collected by suction filtration and washed with THF, water (until pHneutral) and methanol. The obtained solid was dissolved in hotchlorobenzene and filtered through a pad of silica gel. After rinsingwith additional hot chlorobenzene, the filtrate was concentrated underreduced pressure and the resulting precipitate was collected by suctionfiltration and washed with a minimal amount of chlorobenzene. Afterdrying, compound of formula (I) was obtained. Purification was achievedby sublimation.

Synthesis of6-(4-(4-([1,1′-biphenyl]-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyrldine(C-2)

Compound C₂ was synthesized by following general procedure 2. A flaskwas flushed with nitrogen and charged with6-(4-(4,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phen)i)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(4) (5.9 g, 12.8 mmol),2-([1,1′-biphenyl]-2-yl)-4-chloro-6-phenyl-1,3,5-triazine (8) (4.6 g,13.4 mmol), Pd(PPh₃)₄ (0.3 g, 0.26 mmol), and K₂CO₃ (3.5 g, 25.6 mmol).A mixture of deaerated THF/water (4:1, 50 mL) was added and the reactionmixture was heated to reflux under a nitrogen atmosphere for 21 h. Aftercooling down to 5° C. using an ice bath, the formed precipitate wascollected by suction filtration and washed with THF, water (until pHneutral) and methanol. The obtained solid was dissolved in hotchlorobenzene and filtered through a pad of silica gel. After rinsingwith additional hot chlorobenzene, the filtrate was concentrated underreduced pressure and the resulting precipitate was collected by suctionfiltration and washed with a minimal amount of chlorobenzene. Afterdrying, 8 g of a6-(4-(4-([1,1′-biphenyl]-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(C-2) were obtained. Purification was achieved by sublimation. m/z=643([M+H]⁺).

Synthesis of6-(3-(4-([1,1′-biphenyl]-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(C-3)

The general procedure 2 was followed to yield 4.8 g (93% yield) of6-(3-(4-([1,1′-biphenyl]-2-yl)-6-phenyl-1,3,5-triazin-2-yl)phenyl)bis(benzofuro)[3,2-b:2′,3′-e]pyridine(C-3). Purification was achieved by sublimation. m/z=643 ([M+H]⁺).

Synthesis of3′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-4-carbonitrile(C-15)

The general procedure 2 was followed to yield 5.5 g (64% yield) of a3′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-4-carbonitrile(C-15). Purification was achieved by sublimation. m/z=437 ([M+H]⁺).

Synthesis of(4′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-3-yl)dimethylphosphineoxide (C-21)

The general procedure 2 was followed to yield 5.5 g (82% yield) of a(4′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-3-yl)dimethylphosphineoxide (C-21) were obtained. Purification was achieved by sublimation.m/z=488 ([M+H]⁺).

Synthesis of(3′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-4-yl)dimethylphosphineoxide (C-24)

The general procedure 2 was followed to yield 4.1 g (77% yield) of a(4′-(bis(benzofuro)[3,2-b:2′,3′-e]pyridin-6-yl)-[1,1′-biphenyl]-3-yl)dimethylphosphineoxide (C-24) were obtained. Purification was achieved by sublimation.m/z=488 ([M+H]⁺).

Melting Point

The melting point (mp) is determined as peak temperatures from the DSCcurves of the above TGA-DSC measurement or from separate DSCmeasurements (Mettler Toledo DSC822e, heating of samples from roomtemperature to completeness of melting with heating rate 10 K/min undera stream of pure nitrogen. Sample amounts of 4 to 6 mg are placed in a40 μL Mettler Toledo aluminum pan with lid, a <1 mm hole is pierced intothe lid).

Glass Transition Temperature

The glass transition temperature (Tg) is measured under nitrogen andusing a heating rate of 10 K per min in a Mettler Toledo DSC 822edifferential scanning calorimeter as described in DIN EN ISO 31357,published in March 2010.

Reduction Potential

The reduction potential is determined by cyclic voltammetry withpoteniostatic device Metrohm PGSTAT30 and software Metrohm Autolab GPESat room temperature. The redox potentials given at particular compoundswere measured in an argon de-aerated, dry 0.1M THF solution of thetested substance, under argon atmosphere, with 0.1M tetrabutylammoniumhexafluorophosphate supporting electrolyte, between platinum workingelectrodes and with an Ag/AgCl pseudo-standard electrode (Metrohm Silverrod electrode), consisting of a silver wire covered by silver chlorideand immersed directly in the measured solution, with the scan rate 100mV/s. The first run was done in the broadest range of the potential seton the working electrodes, and the range was then adjusted withinsubsequent runs appropriately. The final three runs were done with theaddition of ferrocene (in 0.1M concentration) as the standard. Theaverage of potentials corresponding to cathodic and anodic peak of thestudied compound, after subtraction of the average of cathodic andanodic potentials observed for the standard Fe/Fe redox couple, affordedfinally the values reported above. All studied compounds as well as thereported comparative compounds showed well-defined reversibleelectrochemical behaviour.

Dipole Moment

The dipole moment |{right arrow over (μ)}| of a molecule containing Natoms is given by:

$\overset{\rightarrow}{\mu} = {\sum\limits_{i}^{N}{q_{i}\overset{\rightarrow}{r_{i}}}}$${\overset{\rightarrow}{\mu}} = \sqrt{\mu_{x}^{2} + \mu_{y}^{2} + \mu_{z}^{2}}$

where q_(i) and {right arrow over (r)}_(ι) are the partial charge andposition of atom i in the molecule.

The dipole moment is determined by a semi-empirical molecular orbitalmethod.

The geometries of the molecular structures are optimized using thehybrid functional B3LYP with the 6-31G* basis set in the gas phase asimplemented in the program package TURBOMOLE V6.5. If more than oneconformation is viable, the conformation with the lowest total energy isselected to determine the bond lengths of the molecules.

Calculated HOMO and LUMO

The HOMO and LUMO are calculated with the program package TURBOMOLEV6.5. The optimized geometries and the HOMO and LUMO energy levels ofthe molecular structures are determined by applying the hybridfunctional B3LYP with a 6-31G* basis set in the gas phase. If more thanone conformation is viable, the conformation with the lowest totalenergy is selected.

General Procedure 1 for Fabrication of OLEDs

For top emission devices, for Example 1 and comparative example in table2, a glass substrate was cut to a size of 50 mm×50 mm×0.7 mm,ultrasonically cleaned with isopropyl alcohol for 5 minutes and thenwith pure water for 5 minutes, and cleaned again with UV ozone for 30minutes. 100 nm Ag were deposited on the glass substrate at a pressureof 10-5 to 10-7 mbar to form the anode.

Then, 92 vol.-%Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine(CAS 1242056-42-3) with 8 vol.-%2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile)was vacuum deposited on the anode, to form a HIL having a thickness of 0nm. Then,Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-aminewas vacuum deposited on the HIL, to form a HTL having a thickness of 118nm.

Then,N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)-[1,1′:4′,1″-terphenyl]-4-amine(CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electronblocking layer (EBL) having a thickness of 5 nm.

Then, 97 vol-% Hog (Sun Fine Chemicals) as EML host and 3 vol-% BD200(Sun Fine Chemicals) as fluorescent blue dopant were deposited on theEBL, to form a blue-emitting EML with a thickness of 20 nm.

Then the auxiliary ETL was formed with a thickness of 5 nm by depositingcompound C-2 according to the inventive example 1 and by depositingcompound 1 according to the comparative example 1 on the emission layer(EML).

Then, the electron transporting layer was formed on the auxiliaryelectron transport layer by depositing2-([1,1′-biphenyl]-4-yl)-4-(9,9-diphenyl-9H-fluoren-4-yl)-6-phenyl-1,3,5-triazine(ETM-1) with a thickness of 31 nm. The electron transport layercomprises 50 wt.-% matrix compound and 50 wt.-% of LiQ, see Table 2.

Then, the electron injection layer was formed on the electrontransporting layer by deposing Yb with a thickness of 2 nm.

Ag was evaporated at a rate of 0.01 to 1 Å/s at 10-7 mbar to form acathode with a thickness of 11 nm.

A cap layer ofBiphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-aminewas formed on the cathode with a thickness of 75 nm.

The OLED stack is protected from ambient conditions by encapsulation ofthe device with a glass slide. Thereby, a cavity is formed, whichincludes a getter material for further protection.

General Procedure 2 for Fabrication of OLEDs

For top emission devices, for Example 2 table 3, a glass substrate wascut to a size of 50 mm×50 mm×0.7 mm, ultrasonically cleaned withisopropyl alcohol for 5 minutes and then with pure water for 5 minutes,and cleaned again with UV ozone for 30 minutes. 100 nm Ag were depositedon the glass substrate at a pressure of 10-5 to 10-7 mbar to form theanode.

Then, 92 vol.-%Biphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-amine(CAS 1242056-42-3) with 8 vol.-%2,2′,2″-(cyclopropane-1,2,3-triylidene)tris(2-(p-cyanotetrafluorophenyl)acetonitrile)was vacuum deposited on the anode, to form a HIL having a thickness of10 nm. Then,Biphenyl-4-yl(9,9-diphenyl-9H-Bren-2-yl)-[4-(9-phenyl-H-carbazol-3-yl)phenyl]-aminewas vacuum deposited on the HIL, to form a HTL having a thickness of 118nm.

Then,N,N-bis(4-(dibenzo[b,d]furan-4-yl)phenyl)[1,1′:4′,1″-terphenyl]-4-amine(CAS 1198399-61-9) was vacuum deposited on the HTL, to form an electronblocking layer (EBL) having a thickness of 5 nm.

Then, 97 vol.-% Hog (Sun Fine Chemicals) as EML host and 3 vol.-% BD200(Sun Fine Chemicals) as fluorescent blue dopant were deposited on theEBL, to form a blue-emitting EML with a thickness of 20 nm.

Then the auxiliary ETL was formed with a thickness of 5 nm by depositingcompound 1 on the emission layer (EML).

Then, the electron transporting layer was formed on the auxiliaryelectron transport layer by depositing compound C-2 with a thickness of31 nm. The electron transport layer comprises 50 wt.-% matrix compoundand 50 wt.-% of LiQ, see Table 3.

Then, the electron injection layer was formed on the electrontransporting layer by deposing Yb with a thickness of 2 nm.

Ag was evaporated at a rate of 0.01 to 1 Å/s at 10-7 mbar to form acathode with a thickness of 11 nm.

A cap layer ofBiphenyl-4-yl(9,9-diphenyl-9H-fluoren-2-yl)-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-aminewas formed on the cathode with a thickness of 75 nm.

The OLED stack is protected from ambient conditions by encapsulation ofthe device with a glass slide. Thereby, a cavity is formed, whichincludes a getter material for further protection.

To assess the performance of the inventive examples compared to theprior art, the current efficiency is measured at 20° C. Thecurrent-voltage characteristic is determined using a Keithley 2635source measure unit, by sourcing a voltage in V and measuring thecurrent in mA flowing through the device under test. The voltage appliedto the device is varied in steps of 0.1V in the range between 0V and10V. Likewise, the luminance-voltage characteristics and CIE coordinatesare determined by measuring the luminance in cd/m² using an InstrumentSystems CAS-140CT array spectrometer for each of the voltage values. Thecd/A efficiency at 10 mA/cm2 is determined by interpolating theluminance-voltage and current-voltage characteristics, respectively.

Lifetime LT of the device is measured at ambient conditions (20° C.) and30 mA/cm², using a Keithley 2400 source meter, and recorded in hours.

The brightness of the device is measured using a calibrated photo diode.The lifetime LT is defined as the time till the brightness of the deviceis reduced to 97% of its initial value.

The light output in external efficiency EQE and power efficiency (lm/Wefficiency) are determined at 10 mA/cm2 for top emission devices.

To determine the efficiency EQE in % the light output of the device ismeasured using a calibrated photodiode.

To determine the power efficiency in lm/W, in a first step the luminancein candela per square meter (cd/m2) is measured with an arrayspectrometer CAS140 Cr from Instrument Systems which has been calibratedby Deutsche Akkreditierungs¬stelle (DAkkS). In a second step, theluminance is then multiplied by a and divided by the voltage and currentdensity.

Technical Effect of the Invention

The compounds according to formula (I) and the organic electronicdevices comprising an organic semiconducting layer comprising or made ofa compound of formula (I) solve the problem underlying the presentinvention by being superior over the organic electroluminescent devicesand compounds known in the art, in particular to improve the lifetime(LT97, 30 mA/cm²) of the respective device.

The beneficial effect of the invention on the performance of organicelectronic devices can be seen in Table 2 and Table 3. As can be seen inTable 2, the performance of the organic electronic devices of theinventive examples 1 with respect to lifetime (LT97, 30 mA/cm²) isimproved as compare to the comparative example 1.

TABLE 1 Properties of comparative example 1 and compound of formula (I)Diplole mp Tg T_(RO) HOMO LUMO moment Referred to as: Structure (° C.)(° C.) (° C.) (eV) (eV) (Debye) Comparative example 1 Compound 1

— 141 267 −5.72 −1.82 0.30 Example 1 C1

289 159 256 −5.82 −1.63 1.61 Example 2 C2

331 129 266 −6.01 −2.08 0.73 C-3

322 117 259 −5.87 −1.87 0.93 C-15

305 94 208 −6.01 −1.89 5.04 C-21

294 115 226 −5.84 −2.76 4.42 C-24

302 118 234 −5.95 −1.78 3.68

TABLE 2 Performance of an organic electroluminescent device comprisingan electron transport layer 1 comprising a compound of formula (I)Compound Concentration Concentration Thickness Operating cd/A in ofmatrix of alkali electron voltage efficiency LT97 at electron Thicknesscompound in Alkali organic transport at 10 at 10 30 transport ETL-1Matrix ETL-2 organic complex layer 2 mA/cm² mA/cm² mA/cm² layer 1 (nm)compound (vol.-%) complex (vol.-%) (nm) (V) (cd/A) (h) ComparativeCompound 5 ETM-1 50 LiQ 50 31 3.5 8.4 42 example 1 1- Example 1 C-1 5ETM-1 50 LiQ 50 31 3.7 7.6 61 The features disclosed in the foregoingdescription and in the dependent claims may, both separately and in anycombination thereof, be material for realizing the aspects of thedisclosure made in the independent claims, in diverse forms thereof.

TABLE 3 Performance of an organic electroluminescent device comprisingan electron transport layer-2 comprising a compound of formula 1Concentration Concentration Operating cd/A of matrix of alkali voltageefficiency LT97 at compound in Alkali organic Thickness at 10 at 10 30Matrix ETL 2 organic complex ETL-2 mA/cm² mA/cm² mA/cm² compound(vol.-%) complex (vol.-%) (nm) (V) (cd/A) (h) Example 2 C-2  50 LiQ 5031 3.7 6.05  96 Example 3 C-3  50 LiQ 50 31 3.6 7.6  100 Example 4 C-1550 LiQ 50 31 3.6 7.2   65 The features disclosed in the foregoingdescription and in the dependent claims may, both separately and in anycombination thereof, be material for realizing the aspects of thedisclosure made in the independent claims, in diverse forms thereof.

The features disclosed in the foregoing description and in the dependentclaims may, both separately and in any combination thereof, be materialfor realizing the aspects of the disclosure made in the independentclaims, in diverse forms thereof.

1. Organic electronic device comprising an anode, a cathode, aphotoactive layer and an organic semiconductive layer, wherein theorganic semiconductive layer is arranged between the photoactive layerand the cathode, wherein the organic semiconductive layer comprises acompound represented by the following formula (I):HAr-L-Ar₁—(—R¹)_(m)  (I) wherein HAr is a group represented by one ofthe following formulas (II to IV)

wherein the asterisk symbol “*” represents the binding position of thegroup HAr to the moiety L and; wherein X may be the same or differentfrom each other and are independently selected from O and S; L isselected from the group consisting of unsubstituted or substituted C₆ toC₂₄ arylene and unsubstituted or substituted C₃ to C₂₄ heteroarylene,wherein the one or more substituents, if present, are independentlyselected from the group consisting of hydrogen, C₆ to C₁₈ aryl, C₃ toC₂₅ heteroaryl, D, F, CN, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆alkyl, C₁ to C₁₆ alkoxy, C₁ to C₁₇ alkoxy, C₁ to C₁₆ alkoxy, nitrile and—PO(R³)₂, wherein R³ are independently selected from C₁ to C₁₆ alkyl, C₆to C₁₈ aryl or C₃ to C₂₅ heteroaryl; Ar₁ is selected from the groupconsisting of C₆ to C₆₀ arylene, C₃ to C₅₀ heteroarylene containing atleast one heteroatom selected from O, N, S, Si and P, and the followinggroups represented by the formulas V to VII;

and the one or more R¹ and R² are independently selected from the groupconsisting of hydrogen, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, D, F, CN,C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, C₁to C₁₆ alkoxy, C₁ to C₁₆ alkoxy, nitrile and —PO(R³)₂, wherein the groupR³ is selected from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅heteroaryl; wherein m is an integer from 0 to 5; n is independently aninteger from 0 to 4; and wherein if one or more of HAr, Ar¹, L, R¹, R²and R³ and substituent on one or more of HAr, Ar¹, and L is a carboncontaining group comprising at least one carbon atom directly connectedwith at least one hydrogen atom, the hydrogen atoms comprised in thecarbon-containing group may be partially or fully replaced by deuteriumatoms and/or fluorine atoms.
 2. Organic electronic device according toclaim 1, wherein the organic semiconductive layer is an electrontransport layer and/or an electron injection layer.
 3. Organicelectronic device according to claim 1, wherein the organicsemiconductive layer further comprises a metal, a metal salt, an organicalkali metal complex or mixtures thereof.
 4. Organic electronic deviceaccording to claim 1, wherein the organic semiconductive layer isnon-emissive.
 5. Organic electronic device according to claim 1, whereinthe organic semiconductive layer is an auxiliary electron transportlayer.
 6. Organic electronic device according to claim 1, wherein L isselected from unsubstituted or substituted C₆ to C₂₄ arylene andunsubstituted or substituted C₃ to C₂₄ heteroarylene.
 7. Organicelectronic device according to claim 1, wherein Ar₁ is independentlyselected from the group consisting of phenylene, napthylene,phenantrhylene, anthracenylene, fluoranthenylene, pyrenylene,fluoenylene, pyridinylene, bipyridinylene, terpyridinylene,phenanthrolinylene, pyrimidinylene, pyrazinylene, triazinylene,quinolinylene, benzoquinolinylene, quinoxalinylene,benzoquinoxalinylene, acridinylene, benzoacridinylene,dibenzoacridinylene, phenanthrolinylene, carbazolenylene,dibenzofuranenylene, dibenzothiophenylene, benzofuropyrimidinylene,benzothienopyrimidinylene.
 8. Organic electronic device according toclaim 1, wherein Ar₁ is selected from the group of compounds representedby the formulas V to VII


9. Organic electronic device according to claim 1, wherein R¹ isindependently selected from the group consisting of hydrogen, C₆ to C₁₈aryl, C₃ to C₂₅ heteroaryl, F, CN and PO(R³)₂, wherein R³ is selectedfrom C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅ heteroaryl. 10.Organic electronic device according to claim 1, wherein m is an integerfrom 1 to
 4. 11. Compound represented by the following formula (I)HAr-L-Ar¹—(—R¹)_(m)  (I) wherein HAr is a group represented by one ofthe following formulas (II to IV)

wherein the asterisk symbol “*” represents the binding position of thegroup HAr to the moiety L and; wherein X may be the same or differentfrom each other and are independently selected from O and S; L isselected from the group consisting of unsubstituted or substituted C₆ toC₂₄ arylene and unsubstituted or substituted C₃ to C₂₄ heteroarylene,wherein the one or more substituents, if present, are independentlyselected from the group consisting of hydrogen, C₆ to C₁₈ aryl, C₃ toC₂₄ heteroaryl, D, F, CN, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, partially orfully deuterated C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, C₁ to C₁₇ alkoxy, C₁to C₁₆ alkoxy, nitrile and —PO(R³)₂, wherein R³ are independentlyselected from C₁ to C₁₆ alkyl, C₆ to C₁₈ aryl or C₃ to C₂₅ heteroaryl;Ar₁ is selected from the group consisting of C₆ to C₆₀ arylene, C₃ toC₅₀ heteroarylene containing at least one heteroatom selected from O, N,S, Si and P, and the following groups represented by the formulas V toVII;

and the one or more R¹ and R² are independently selected from the groupconsisting of hydrogen, C₆ to C₁₈ aryl, C₃ to C₂₅ heteroaryl, D, F, CN,C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkyl, C₁ to C₁₆ alkoxy, C₁to C₁₆ alkoxy, partially or fully deuterated C₁ to C₁₆ alkoxy, nitrileand —PO(R³)₂, wherein the group R³ is selected from C₁ to C₁₆ alkyl, C₆to C₁₈ aryl and C₃ to C₂₅ heteroaryl; m is an integer from 0 to 5; n isindependently an integer from 0 to 4; and wherein if one or more of HAr,Ar¹, L, R¹, R² and R³ and substituent on one or more of HAr, Ar¹, and Lis a carbon containing group comprising at least one carbon atomdirectly connected with at least one hydrogen atom, the hydrogen atomscomprised in the carbon-containing group may be partially or fullyreplaced by deuterium atoms and/or fluorine atoms. provided that if L isa trivalent group than the compound of formula (I) is not symmetrical;and provided that if Ar₁ is a carbazolylene group than L is notphenylene.
 12. Compound according to claim 11, wherein L is selectedfrom unsubstituted or substituted C₆ to C₂₄ arylene and unsubstituted orsubstituted C₃ to C₂₄ heteroarylene.
 13. Compound according to claim 11,wherein Ar₁ is selected from the group of compounds represented by theformulas V to VII


14. Compound according to claim 1, wherein R¹ and R² is independentlyselected from the group consisting of hydrogen, C₆ to C₁₈ aryl, C₃ toC₂₅ heteroaryl, F, CN and PO(R³)₂, wherein R³ is selected from C₁ to C₁₆alkyl, C₆ to C₁₈ aryl and C₃ to C₂₅ heteroaryl.
 15. Compound accordingto claim 11, wherein m is an integer from 1 to 4.